CN106463783A - Nickel-zinc battery - Google Patents

Abstract

Provided is a highly reliable nickel-zinc battery which uses a separator having hydroxide ion conductivity but not permeability. This nickel-zinc battery is equipped with: a positive electrode containing a nickel hydroxide and/or a nickel oxyhydroxide; a positive electrode electrolyte containing an alkali metal hydroxide and having the positive electrode immersed therein; a negative electrode containing zinc and/or zinc oxide; a negative electrode electrolyte containing an alkali metal hydroxide and having the negative electrode immersed therein; a sealed container for housing the positive electrode, the positive electrode electrolyte, the negative electrode, and the negative electrode electrolyte; and a separator having hydroxide ion conductivity but not permeability, and provided in the sealed container so as to demarcate a positive electrode chamber for housing the positive electrode and the positive electrode electrolyte, and a negative electrode chamber for housing the negative electrode and the negative electrode electrolyte.

Description

Nickel-zinc cell

Technical field

The present invention relates to a kind of nickel-zinc cell.

Background technology

Although all developing and studying Ni-MH secondary battery all the time, not yet practical.Reason is that presence is as follows Problem：The zinc constituting negative pole during charging generates the ingotism being referred to as dendrite, and this dendrite punctures dividing plate, short with positive pole generation Road.On the other hand, nickel-cadmium cell and Ni-MH battery commercialization.However, Ni-MH secondary battery has high theoretical capacity Density, higher about 5 times than NI-G secondary cell, higher 2.5 times than nickel-hydrogen secondary cell, higher 1.3 times than lithium ion battery, and, have There is the relatively low such advantage of cost of material.Therefore, for Ni-MH secondary battery, being strongly desired to develop prevents zinc dendrite from leading to Short circuit technology.

For example in patent documentation 1 (International Publication No. 2013/118561), in order to prevent short circuit that zinc dendrite leads to Purpose is it is proposed that positive pole and negative pole will be arranged on by the dividing plate that hydroxide ion conductive inorganic solid electrolyte body is formed Between Ni-MH secondary battery.Disclose in the publication：The relative density of this inorganic solid electrolyte body is more than 90%, can With by basic composition is formula：M²⁺ _1-xM³⁺ _x(OH)₂A^n- _x/n·mH₂O (in formula, M²⁺For divalent cation more than at least one, M³⁺ For trivalent cation more than at least one, A^n-For the anion of n valency, n is more than 1 integer, and x is 0.1～0.4) stratiform double Hydroxide is formed.

In addition it is also known that hermetic type nickel-zinc cell in the oxygen that negative pole absorbs and cycle charging latter stage produces.For example exist Disclose in patent documentation 2 (Japanese Unexamined Patent Publication 5-303978 publication) and possess pole plate group and configuration around this pole plate group The hermetic type nickel-zinc cell of guarantor's liquid layer, described pole plate group has positive plate, negative plate, dividing plate and keeper, and discloses guarantor's liquid Layer is the layer containing electrolyte in length 0.5～50mm, the cellulose fibre of 5～100 μm of diameter.In this patent documentation 2, Using by polypropylene porous film with surfactant process obtained by dividing plate.In patent documentation 3 (Japanese Unexamined Patent Publication 6-96795 Publication) in, disclose a kind of hermetic type nickel-zinc cell, the pad-face of configuration poling group and battery groove bottom to and electrolyte Volume exceedes the 98% of the gross space volume of pole group and below 110%, microporosity film and cellophane film can be used as dividing plate.

It is also known that the oxygen being produced by positive pole in overcharge easily reaches the technology of negative pole via dividing plate.For example in patent Disclose by the hydrophobic resin that at least there is hydrophilic fibre on surface in document 4 (Japanese Unexamined Patent Publication 5-36394 publication) The separator for alkaline cell that porous body film is formed.

Prior art literature

Patent documentation

Patent documentation 1：International Publication No. 2013/118561

Patent documentation 2：Japanese Unexamined Patent Publication 5-303978 publication

Patent documentation 3：Japanese Unexamined Patent Publication 6-96795 publication

Patent documentation 4：Japanese Unexamined Patent Publication 5-36394 publication

Content of the invention

Nowadays the present inventor etc. find that the dividing plate using having hydroxide ion conductivity but not having water penetration can carry For the high nickel-zinc cell of reliability.

Therefore, it is an object of the invention to, provide a kind of reliability high nickel-zinc cell, it use with hydroxide Ionic conductivity but there is no the dividing plate of water penetration.

According to a scheme of the present invention, provide a kind of nickel-zinc cell, it comprises：

Positive pole, described positive pole contains nickel hydroxide and/or hydroxy nickel oxide,

Anode electrolyte, described anode electrolyte contains alkali metal hydroxide, impregnates described positive pole,

Negative pole, described negative pole contains zinc and/or zinc oxide,

Electrolyte liquid, described electrolyte liquid contains alkali metal hydroxide, impregnates described negative pole,

Hermetic container, described hermetic container accommodates described positive pole, described anode electrolyte, described negative pole and described negative electricity Solution liquid,

Dividing plate, described dividing plate has hydroxide ion conductivity but does not have water penetration, sets in described hermetic container It is set to and will accommodate the cathode chamber of described positive pole and described anode electrolyte and accommodate the negative of described negative pole and described electrolyte liquid Pole room zoning is opened.

Brief description

Fig. 1 is the schematic diagram schematically showing one of nickel-zinc cell of present invention example, represents electric discharge last current state.

Fig. 2 is the figure of the fully charged state representing the nickel-zinc cell shown in Fig. 1.

Fig. 3 is the schematic diagram schematically showing one of the cascade type nickel-zinc cell arranged side by side of present invention example, represents electric discharge end State.

Fig. 4 is the diagrammatic cross-sectional view of a scheme representing the dividing plate being accompanied with porous substrate.

Fig. 5 is the diagrammatic cross-sectional view of another scheme representing the dividing plate being accompanied with porous substrate.

Fig. 6 is the schematic diagram representing layered double-hydroxide (LDH) platy particles.

Fig. 7 is the SEM image on the surface of oxidation aluminum porous substrate making in example 1.

Fig. 8 is to be directed to the XRD spectrum that the crystalline phase of sample obtains in example 1.

Fig. 9 is the SEM image representing the surface micro-structure of film sample observed in example 1.

Figure 10 is the SEM image grinding section micro structure of the composite sample observed in example 1.

Figure 11 A is the exploded perspective view that used in example 1, compactness differentiates mensure system.

Figure 11 B is the diagrammatic cross-sectional view that used in example 1, compactness differentiates mensure system.

Specific embodiment

Nickel-zinc cell

One of nickel-zinc cell of present invention example is schematically shown in Fig. 1.Nickel-zinc cell shown in Fig. 1 is for before being charged A-stage, be equivalent to electric discharge last current state.But, the nickel-zinc cell of the present invention can certainly be constituted with fully charged state. As shown in figure 1, the nickel-zinc cell 10 of the present invention has positive pole 12, anode electrolyte 14, negative pole 16, negative pole in hermetic container 22 Electrolyte 18 and dividing plate 20.Positive pole 12 comprises nickel hydroxide and/or hydroxy nickel oxide.Anode electrolyte 14 comprises alkali metal hydrogen Oxide, impregnates positive pole 12.Negative pole 16 comprises zinc and/or zinc oxide.Electrolyte liquid 18 comprises alkali metal hydroxide, dipping Negative pole 16.Hermetic container 22 accommodates positive pole 12, anode electrolyte 14, negative pole 16 and electrolyte liquid 18.Positive pole 12 and positive electrical Solution liquid 14 might not to be separated it is also possible to be configured to the anode mixture that positive pole 12 and anode electrolyte 14 mix.Equally Ground, negative pole 16 and electrolyte liquid 18 might not to be separated it is also possible to be configured to negative pole 16 and electrolyte liquid 18 mix and The cathode agent becoming.As needed positive electrode collector 13 is arranged to contact with positive pole 12.In addition, as needed by negative pole current collection Body 17 is arranged to contact with negative pole 16.

Dividing plate 20 is arranged to accommodate the cathode chamber 24 of positive pole 12 and anode electrolyte 14 and accommodate in hermetic container 22 Anode chamber 26 zoning of negative pole 16 and electrolyte liquid 18 is opened.Dividing plate 20 has hydroxide ion conductivity, but does not have Aqueouss.Herein, " there is no water penetration " in this specification and refer to " the fine and close sex determination test " being used by aftermentioned example 1 or with In the case of method on the basis of this or composition evaluation water penetration, with measuring object (such as dividing plate 20 and/or porous substrate 28) water of one side side contacts is not transmitted through another surface side.That is, dividing plate 20 does not have water penetration means that dividing plate 20 has not The high compaction of permeable degree is not it is meant that be to have the porous membrane of water penetration or other porous material.Therefore, become right Physical property stops the dividing plate that when charging, the zinc dendrite that generates is led to from running through, thus prevent positive and negative interpolar short circuit extremely effective Constitute.But naturally it is also possible to as shown in Figure 1 porous substrate 28 be set up on dividing plate 20.In a word, because dividing plate 20 has hydrogen-oxygen Compound ionic conductivity, so between anode electrolyte 14 and electrolyte liquid 18, required hydroxide ion can have Efficient move, thus realizing the discharge and recharge reaction in cathode chamber 24 and anode chamber 26.Charge in cathode chamber 24 and anode chamber 26 When reaction as follows, exoelectrical reaction is in contrast.

- positive pole：Ni(OH)₂+OH^-→NiOOH+H₂O+e^-

- negative pole：ZnO+H₂O+2e^-→Zn+2OH^-

Wherein, above-mentioned negative reaction is made up of 2 following reactions.

The dissolving reaction of-ZnO：ZnO+H₂O+2OH^-→Zn(OH)₄ ^2-

The evolution reaction of-Zn：Zn(OH)₄ ^2-+2e^-→Zn+4OH^-

Nickel-zinc cell 10 preferably has side of the positive electrode remaining space 25, the appearance of this side of the positive electrode remaining space 25 in cathode chamber 24 The long-pending water quantities increase and decrease allowing to produce with positive pole reaction during discharge and recharge, and, it is remaining to have negative side in anode chamber 26 Space 27, the volume of this negative side remaining space 27 allows the water quantities producing with negative reaction during discharge and recharge to subtract increasing. (for example leak thus, it is possible to be effectively prevented the unfavorable condition producing because of the water quantities increase and decrease in cathode chamber 24 and anode chamber 26 Container deformation that the intrinsic pressure change of liquid, container leads to etc.), improve the reliability of nickel-zinc cell further.That is, can by above-mentioned reaction equation Know, in cathode chamber 24 during charging, water increases, and in anode chamber 26, water reduces.On the other hand, in cathode chamber 24 during electric discharge, water reduces, And water increases in anode chamber 26.For this point, because nearly all having water penetration, water energy is enough via dividing plate for existing dividing plate Free in and out.But, dividing plate 20 used in the present invention is because the high structure of the compactness with water penetration, water Can not free in and out via dividing plate 20, with discharge and recharge, cathode chamber 24 in and/or the increasing of anode chamber 26 Inner electrolysis liquid measure folk prescription Plus it may occur that a problem that leakage.Therefore, by having side of the positive electrode remaining space 25 in cathode chamber 24, this side of the positive electrode remains The volume of complementary space 25 allows the water quantities increase and decrease producing with positive pole reaction during discharge and recharge, as shown in Fig. 2 being capable of conduct The buffering that when can tackle charging, anode electrolyte 14 increases works.That is, as shown in Fig. 2 side of the positive electrode remaining space after full charge 25 also serve as buffering works, and thus enables that the anode electrolyte 14 of increase will not overflow and be positively held in cathode chamber 24 Interior.Similarly, by having negative side remaining space 27 in anode chamber 26, the volume of this negative side remaining space 27 allows companion The water quantities producing with negative reaction during discharge and recharge subtracts increasing, can increase as electrolyte liquid 18 when can tackle electric discharge Buffering works.

The increase and decrease amount of the moisture in cathode chamber 24 and anode chamber 26 can be calculated based on aforesaid reaction equation.By aforesaid anti- Formula is answered to understand, the H at positive pole 12 during charging₂O growing amount is equivalent to the H at negative pole 16₂2 times of O consumption.Therefore, it can Make the volumetric ratio negative side remaining space 27 of side of the positive electrode remaining space 25 big.In a word, preferably make the appearance of side of the positive electrode remaining space 25 Amass for have some or to a certain degree have more than needed volume so as to be not only contained in the moisture incrementss estimate in cathode chamber 24 moreover it is possible to The enough oxygen can be produced by positive pole 12 when gas, the overcharges such as pre-existing air in suitable intrinsic pressure receiving cathode chamber 24 Gas.As long as although it may be said that negative side remaining space 27 is identical with side of the positive electrode remaining space 25 as shown in Figure 1 for this point The volume of degree, but when being constituted battery with last current state of discharging, be preferably provided with exceeding the water decrement producing with charging Remaining space.In a word, negative side remaining space 27, can because the increase and decrease amount of water only has the half degree in cathode chamber 24 With less than side of the positive electrode remaining space 25.

Nickel-zinc cell 10 be electric discharge last current state under construct in the case of, preferably：Side of the positive electrode remaining space 25 has and exceedes Estimate the volume of the water quantities increasing with positive pole reaction when charging, be not pre-charged with side of the positive electrode remaining space 25 Anode electrolyte 14, and, negative side remaining space 27 has to exceed and estimates the water that reduces with negative reaction when charging The volume of component, is pre-charged with the electrolyte liquid 18 of the amount estimating minimizing in negative side remaining space 27.On the other hand, nickel Zinc battery 10 be construct under fully charged state in the case of, preferably：Side of the positive electrode remaining space 25 has to exceed to be estimated with putting The volume of the water quantities that positive pole when electric reacts and reduces, is pre-filled with the amount estimating minimizing in side of the positive electrode remaining space 25 Anode electrolyte 14, and, negative side remaining space 27 have exceed estimate with electric discharge when negative reaction and increase The volume of water quantities, is not pre-charged with electrolyte liquid 18 in negative side remaining space 27.

In side of the positive electrode remaining space 25, preferably it is not filled with positive pole 12 and/or be not filled with bearing in negative side remaining space 27 Pole 16, does not more preferably fill positive pole 12 and negative pole 16 in side of the positive electrode remaining space 25 and negative side remaining space 27 respectively. In these remaining spaces, the electrolyte leading to because water quantities reduces during discharge and recharge, can be occurred to exhaust.That is, because surplus at these Even if being filled with positive pole 12, negative pole 16 in complementary space, it also cannot be made fully to participate in discharge and recharge reaction, thus inefficent.Cause This, by being not filled with positive pole 12 and negative pole 16 respectively in side of the positive electrode remaining space 25 and negative side remaining space 27, can make Positive pole 12 and negative pole 16 no waste and more efficiently and stably participate in cell reaction.

The nickel-zinc cell of the present invention is preferably configured as the longitudinally disposed longitudinal type structure of dividing plate.In the longitudinally disposed situation of dividing plate Under, become cathode chamber/dividing plate/anode chamber composition that laterally (horizontal direction) arranges.The feelings of longitudinally disposed dividing plate 20 as shown in Figure 1 Under condition, typical scenario is：There is above cathode chamber 24 side of the positive electrode remaining space 25, and, have above anode chamber 26 There is negative side remaining space 27.But, in the case of using gelatinous electrolyte, even if electrolyte reduces, remain able to Keep electrolyte in the discharge and recharge reaction part of cathode chamber 24 and/or anode chamber 26, so can also be above cathode chamber 24 Part (such as lateral portions beyond part (such as lateral portions or section below) in addition and/or the top of anode chamber 26 Or section below) side of the positive electrode remaining space 25 and/or negative side remaining space 27 are set, the degree of freedom of design increases.

Or, the nickel-zinc cell of the present invention can also be configured to the cross structure of dividing plate horizontally set.Laterally set in dividing plate In the case of putting, become cathode chamber/dividing plate/anode chamber composition that longitudinally (vertical direction) is laminated.Now, for example by using solidifying Gluey electrolyte, even if electrolyte reduces it is also possible to remain the contact that dividing plate is with electrolyte.Alternatively, it is also possible to constitute For：Between positive pole and dividing plate and/or between negative pole and dividing plate, the water-absorbing resins such as configuration non-woven fabrics or guarantor's fluidity are resinous Second partition (resin separator), even if can also be maintained at positive pole and/or negative pole by electrolyte in the case that electrolyte reduces Discharge and recharge reaction part.As the preference of water-absorbing resins or guarantor's fluidity resin, polyolefin-based resins can be enumerated.So Can above cathode chamber beyond part (such as lateral portions or section below) and/or the portion beyond the top of anode chamber Divide (such as lateral portions or section below) setting side of the positive electrode remaining space and/or negative side remaining space.

Dividing plate

Dividing plate 20 is to have hydroxide ion conductivity but does not have the part of water penetration it is typical that tabular, membranaceous Or the form of stratiform.Dividing plate 20 is arranged in hermetic container 22, will accommodate cathode chamber 24 He of positive pole 12 and anode electrolyte 14 Accommodate negative pole 16 and anode chamber 26 zoning of electrolyte liquid 18 is opened.

Dividing plate 20 is preferably formed by inorganic solid electrolyte body.Use the conductive nothing of hydroxide ion as dividing plate 20 The electrolyte of positive and negative interpolar is thus isolated, and is guaranteed hydroxide ion conductivity by machine solid electrolytic plastid.And, because Inorganic solid electrolyte for constituting dividing plate 20 is typically fine and close and hard inoganic solids it is possible to physical property stops charging The dividing plate that the zinc dendrite of Shi Shengcheng leads to runs through, thus preventing the short circuit of positive and negative interpolar.As a result, it is possible to nickel zinc is significantly increased The reliability of battery.Inorganic solid electrolyte body is preferably densified to the degree without water penetration.Such as inoganic solids electricity Solution plastid is preferably more than 90%, more preferably more than 92% by the relative density that Archimedes method calculates, further preferably For more than 95%, as long as the fine and close and hard inorganic solid electrolyte body to the degree preventing zinc dendrite from running through, do not limit Due to this.Such fine and close and hard inorganic solid electrolyte body can manufacture through hydrothermal treatment consists.Therefore, not through hydro-thermal The simple powder compact processing is because not fine and close, frangible in the solution, thus as the present invention inorganic solid electrolyte body simultaneously Undesirable.It is however also possible to without hydrothermal treatment consists, as long as densification and hard inorganic solid electrolyte body can be obtained, own Preparation method all can use.

Dividing plate 20 or inorganic solid electrolyte body can be to comprise inoganic solids conductive with hydroxide ion Electrolyte and the particle group that constitutes and assist the densification of these particle groups, the complex of the auxiliary element of solidification.Or, dividing plate 20 can also be as the open pore porous body of base material and separate out in hole and grow and fill this porous body hole inorganic The complex of solid electrolyte (such as layered double-hydroxide).As the example of the material constituting this porous body, can enumerate The insulating properties materials such as the potteries such as aluminium oxide, zirconium oxide, the porous sheet being formed by Foamex or fibrous material.

Inorganic solid electrolyte body preferably comprises with formula：M²⁺ _1-xM³⁺ _x(OH)₂A^n- _x/n·mH₂O (in formula, M²⁺For divalent Cation, M³⁺For the cation of trivalent, A^n-For the anion of n valency, n is more than 1 integer, and x is any for 0.1～0.4, m Real number) basic composition layered double-hydroxide (LDH), more preferably formed by such LDH.In above-mentioned formula, M²⁺Can Think arbitrary divalent cation, as preference, Mg can be enumerated²⁺、Ca²⁺And Zn²⁺, more preferably Mg²⁺.M³⁺Can be for appointing The trivalent cation of meaning, as preference, can enumerate Al³⁺Or Cr³⁺, more preferably Al³⁺.A^n-Can be arbitrary anion, As preference, OH can be enumerated^-And CO₃ ^2-.Therefore, in above-mentioned formula, preferably M²⁺Comprise Mg²⁺、M³⁺Comprise Al³⁺、A^n-Comprise OH^-And/or CO₃ ^2-.N is more than 1 integer, preferably 1 or 2.X is 0.1～0.4, preferably 0.2～0.35.M is arbitrary Real number.More specifically, m is more than 0 it is typical that the real number more than 0 or more than 1 or integer.In addition, in above-mentioned formula, can With with the cation of 4 valencys or higher valence mumber by M³⁺Part or all of replacement, at this time it is also possible to suitably change in above-mentioned formula Anion A^n-Coefficient x/n.

Inorganic solid electrolyte body preferably implements densification by hydrothermal treatment consists.Hydrothermal treatment consists double hydroxides to stratiform The one densification of thing, especially Mg-Al type layered double-hydroxide is very effective.Implement densification by hydrothermal treatment consists for example such as Patent documentation 1 (International Publication No. 2013/118561) is described, puts into the powder compact of pure water and tabular in pressure vessel, Carry out 2～24 hours, preferably 3～10 hours at a temperature of 120～250 DEG C, preferably 180～250 DEG C.Using hydrothermal treatment consists More preferably manufacture method is as described later.

Inorganic solid electrolyte body can be any one form in tabular, membranaceous or stratiform, membranaceous or lamellar morphologies In the case of, preferably the inorganic solid electrolyte body of membranaceous or stratiform is formed on porous substrate or wherein.If tabular shape State, then be able to ensure that sufficient compactedness, and more effectively stops zinc dendrite from running through.On the other hand, if thickness compares plate The form of the thin membranaceous or stratiform of shape, then have the following advantages：It is able to ensure that and stop zinc dendrite from running through required MIN knot Solidity, and have a mind to reduce the resistance of dividing plate.The preferred thickness of the inorganic solid electrolyte body of tabular is 0.01～0.5mm, more It is preferably 0.02～0.2mm, more preferably 0.05～0.1mm.In addition, the hydroxide ion of inorganic solid electrolyte body Conductivity is more desirable, and typically has 10^-4～10^-1The conductivity of S/m.On the other hand, the situation of membranaceous or lamellar morphologies Under, thickness be preferably less than 100 μm, more preferably less than 75 μm, more preferably less than 50 μm, particularly preferably 25 μm with Under, most preferably less than 5 μm.By making it so thin, it is capable of the low resistance of dividing plate 20.Because the lower limit root of thickness Different according to purposes, so being not particularly limited, but in order to ensure as the knot to a certain degree required by separator membrane or layer Solidity, preferred thickness is more than 1 μm, more preferably more than 2 μm.

Porous substrate 28 can be set in the one or two sides of dividing plate 20.In the one side of dividing plate 20, porous substrate 28 is set In the case of, porous substrate 28 can be located at the surface of negative pole 16 side of dividing plate 20 it is also possible to be located at positive pole 12 side of dividing plate 20 Surface.Because porous substrate 28 has water penetration, anode electrolyte 14 and electrolyte liquid 18 can reach dividing plate certainly 20, but by there is porous substrate 28, hydroxide ion can more stably be kept on dividing plate 20.In addition, because energy Enough by porous substrate 28 give intensity, so also can thinning dividing plate 20 and realize low resistance.Alternatively, it is also possible in porous On base material 28 or wherein form dense film or the compacted zone of inorganic solid electrolyte body (preferably LDH).List in dividing plate 20 Face setting porous substrate in the case of it is considered to prepare porous substrate, on this porous substrate by inorganic solid electrolyte film forming Method (the method is as described later).On the other hand, it is considered to more than 2 in the case of the two sides of dividing plate 20 setting porous substrate Clamp the material powder of inorganic solid electrolyte between the base material of hole and carry out densification.Should illustrate, in FIG, porous substrate On the whole face of 28 one sides being arranged on dividing plate 20 but it is also possible to be the part being provided only in the one side of dividing plate 20 (for example Participate in discharge and recharge reaction region) composition.For example become on porous substrate 28 or wherein by the inorganic solid electrolyte bodily form In the case of membranaceous or stratiform, because its preparation method, typical scenario is that the whole face of one side of dividing plate 20 is provided with porous substrate 28 Constitute.On the other hand, in the case of the inorganic solid electrolyte bodily form being become the tabular of (not needing base material) self-support, can be only A part (such as participating in the region of discharge and recharge reaction) in the one side of dividing plate 20 installs porous substrate 28 afterwards it is also possible in list Porous substrate 28 is installed after on the whole face in face.

In addition, as set forth above, it is possible to configuring nonwoven between positive pole 12 and dividing plate 20 and/or between negative pole 16 and dividing plate 20 The water-absorbing resins such as cloth or guarantor's resinous second partition of fluidity (resin separator) are even and if become situation about reducing in electrolyte Electrolyte can also be maintained at down the composition of the reactive moieties of positive pole and/or negative pole.As water-absorbing resins or Bao Yexingshu The preference of fat, can enumerate polyolefin-based resins.

Positive pole

Positive pole 12 comprises nickel hydroxide and/or hydroxy nickel oxide.For example nickel zinc is being constituted with the electric discharge last current state shown in Fig. 1 In the case of battery, as long as nickel hydroxide is used as positive pole 12, nickel-zinc cell is being constituted with the fully charged state shown in Fig. 2 In the case of, as long as hydroxy nickel oxide is used as positive pole 12.Nickel hydroxide and hydroxy nickel oxide (hereinafter referred to as nickel hydroxide Deng) it is the positive active material being generally used for nickel-zinc cell, typically particle shape.In nickel hydroxide etc., can be brilliant at it Xenogenesis element beyond solid solution has nickel in lattice, thus, it is possible to realize the raising of charge efficiency under high temperature.As such xenogenesis unit The example of element, can enumerate zinc and cobalt.In addition, nickel hydroxide etc. can be mixed with cobalt set member, as such cobalt set member Example, metallic cobalt, the shot-like particle of cobalt/cobalt oxide (such as cobalt black) can be enumerated.And then it is also possible to by nickel hydroxide etc. The surface of particle (can have xenogenesis element with solid solution) is coated to cobalt compound, as the example of such cobalt compound, Ke Yiju Go out cobalt black, the α type cobalt hydroxide of divalent, the β type cobalt hydroxide of divalent, exceed the compound of high-order cobalt of divalent and they Combination in any.

Positive pole 12 except nickel hydroxide based compound and can be solid-solubilized in nickel hydroxide based compound xenogenesis element in addition to, Can also comprise further to add element.As the example of such additional element, scandium (Sc), lanthanum (La), cerium can be enumerated (Ce), praseodymium (Pr), neodymium (Nd), promethium (Pm), samarium (Sm), europium (Eu), gadolinium (Gd), terbium (Tb), dysprosium (Dy), holmium (Ho), erbium (Er), thulium (Tm), lutecium (Lu), hafnium (Hf), tantalum (Ta), tungsten (W), rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), golden (Au) and hydrargyrum (Hg), And their combination in any.Being not particularly limited containing form of additional element, can be with metallic monomer or metallic compound (example As oxide, hydroxide, halogenide and carbonated) form comprise.Add the metallic monomer comprising to add element or gold In the case of belonging to compound, with respect to nickel hydroxide based compound 100 weight portion, its addition is preferably 0.5～20 weight portion, More preferably 2～5 weight portions.

Positive pole 12 can also be configured to anode mixture by comprising electrolyte etc. further.Anode mixture can comprise hydrogen Conductive material, the binding agent etc. such as magnesium oxide-nickel series compound particles, electrolyte and the carbon particle that comprises as needed.

Preferably positive electrode collector 13 is arranged to contact with positive pole 12.Positive electrode collector 13 can run through close as shown in Figure 1 Close container 22 and extend to outside it, be made up of itself positive terminal or in or beyond hermetic container 22 with addition The composition that the positive terminal of setting connects.As the preference of positive electrode collector 13, the nickel porous such as foaming nickel plate can be enumerated Substrate.In this case, the electrode activities such as nickel hydroxide are comprised preferably for example by being equably coated with nickel porous substrate The pasting and make it be dried making the positive plate being formed by positive pole 12/ positive electrode collector 13 of material.Now, it is also preferred that after to drying Positive plate (i.e. positive pole 12/ positive electrode collector 13) implement pressurized treatments, prevent electrode active material from coming off and improve electrode Density.

Negative pole

Negative pole 16 comprises zinc and/or zinc oxide.As long as zinc has the electro-chemical activity of suitable negative pole, can be with zinc gold Any one form in genus, zinc compound and kirsite comprises.As the preference of negative material, zinc oxide, zinc can be enumerated Metal, calcium zincates etc., the more preferably mixture of zinc metal and zinc oxide.Negative pole 16 be configured to gel it is also possible to Electrolyte is mixed and made into cathode agent.For example pass through to add electrolyte and viscosifier in negative electrode active material, can be held The negative pole of easy gelation.As the example of viscosifier, polyvinyl alcohol, polyacrylate, CMC, alginic acid etc. can be enumerated, poly- third Olefin(e) acid because excellent to the chemical reagent resistance of highly basic, it is advantageous to.

As kirsite, kirsite as mercuryless kirsite known to not mercurous and lead can be used.For example contain The indium of 0.01～0.06 mass %, the bismuth of 0.005～0.02 mass %, the kirsite of the aluminum of 0.0035～0.015 mass % have The effect that suppression hydrogen produces, it is advantageous to.Particularly indium, bismuth are favourable in terms of making discharge performance raising.By kirsite The self-dissolving speed that can slow down in alkaline electrolyte as negative pole, thus suppressing hydrogen to produce, improves safety.

The shape of negative material is not particularly limited, and is preferably made powder, so that surface area increases, copes with Heavy-current discharge.The mean diameter of preferred negative material, in the case of kirsite, is 90～210 μm of scope, if In the range of being somebody's turn to do, then surface area is big, so being suitable for reply heavy-current discharge, and easily equably mixes with electrolyte and gelating agent Close, treatability during battery assembling is also good.

Preferably negative electrode collector 17 is arranged to contact with negative pole 16.Negative electrode collector 17 can run through close as shown in Figure 1 Close container 22 and extend to outside it, be made up of itself negative terminal or in or beyond hermetic container 22 with addition The composition that the negative terminal of setting connects.As the preference of negative electrode collector 17, copper punch metal can be enumerated.This situation Under, such as on copper punch metal, coating comprises Zinc oxide powder and/or zinc powder and desired binding agent is (for example poly- Tetrafluoroethene particle) mixture, can suitably make the negative plate being formed by negative pole 16/ negative electrode collector 17.Now, Pressurized treatments implemented by the dried negative plate of preferred pair (i.e. negative pole 16/ negative electrode collector 17), prevent electrode active material from coming off And raising electrode density.

Electrolyte

Anode electrolyte 14 and electrolyte liquid 18 comprise alkali metal hydroxide.That is, alkali metal hydroxide will be comprised Aqueous solution be used as anode electrolyte 14 and electrolyte liquid 18.As the example of alkali metal hydroxide, hydrogen-oxygen can be enumerated Change potassium, sodium hydroxide, Lithium hydrate, ammonium hydroxide etc., more preferably potassium hydroxide.In order to suppress the self-dissolving of kirsite, permissible Add the zinc compounds such as zinc oxide, zinc hydroxide in the electrolytic solution.As described above, anode electrolyte 14 and electrolyte liquid 18 can To mix with positive pole 12 and/or negative pole 16, existed with the form of anode mixture and/or cathode agent.In addition, in order to prevent from being electrolysed Liquid leaks, can be by Electrolyte Gel.As gelating agent, preferably use the solvent of Electolyte-absorptive and the polymerization of swelling Thing, it is possible to use the polymer such as poly(ethylene oxide), polyvinyl alcohol, polyacrylamide, starch.

Hermetic container

Hermetic container 22 is airtight receiving positive pole 12, the container of anode electrolyte 14, negative pole 16 and electrolyte liquid 18, tool Get everything ready and have fluid tight and bubble-tight structure.As long as the material of hermetic container has resistance to alkali metal hydroxides such as potassium hydroxide Just it is not particularly limited by property, preferably the resin-made such as vistanex, ABS resin, Noryl, more preferably ABS tree Fat or Noryl.Dividing plate 20 can be fixed in hermetic container 22 in various ways, preferably by potassium hydroxide etc. The binding agent that alkali metal hydroxide has toleration is fixed.In addition, use the hermetic container 22 of vistanex In the case of, it is also preferred that passing through heat bonding stationary barrier 20.

Cascade type nickel-zinc cell side by side

Nickel-zinc cell 10 shown in Fig. 1 possesses 1 pair of positive pole 12 and negative pole 16 or possesses 2 in hermetic container 22 Composition to above positive pole 12 and negative pole 16.In this case, preferably positive pole 12 and negative pole 16 alternating juxtaposition are configured to The nickel-zinc cell of cascade type side by side.The one of such cascade type nickel-zinc cell arranged side by side is illustrated in Fig. 3.In figure 3, it is laminated side by side It is negative that type nickel-zinc cell 30 has the first cathode chamber 24a (possessing the positive electrode collector 13 of single spreading positive pole 12)/dividing plate 20/ first Pole room 26a (possessing the negative electrode collector 17 of double spread negative pole 16)/dividing plate 20/ second cathode chamber 24b (is just possessing double spread The positive electrode collector 13 of pole 12)/dividing plate 20/ second anode chamber 26b (possessing the negative electrode collector 17 of double spread negative pole 16)/every The composition that plate 20/ the 3rd cathode chamber 24c (possessing the positive electrode collector 13 of single spreading positive pole 12) is arranged in order.Should say Bright, in figure 3, because the element of cathode chamber 24a, 24b and 24c is identical with the element of the cathode chamber 24 of Fig. 1, Give and Fig. 1 identical symbol, because the element phase of the element of anode chamber 26a and 26b and the anode chamber 26 of Fig. 1 With so giving and Fig. 1 identical symbol.Like this cathode chamber, dividing plate and anode chamber are repeated in desired number of times And appropriately configured, thus may be constructed the cascade type nickel-zinc cell arranged side by side possessing the desired positive pole of quantity and negative pole.

Purposes

The nickel-zinc cell of the present invention can be used for the various uses needing to play its excellent power reservoir capacity.As can apply The example of the preferable use of the nickel-zinc cell of the present invention, can enumerate UPS (uninterrupted power supply(ups)), HEMS (home energy source pipe Reason system), shop (such as 24 HOUR ACCESS shop), BEMS (building energy management system), hospital, data center, wireless base Stand, (in bay) ship, FEMS (factory energy management system), intelligent Community, CEMS (cluster/community energy management system System), large-sized solar electric station (Mega Solar), wind energy turbine set (wind power plant) etc..In these purposes, the nickel zinc of the present invention Battery can play function as stand-by power supply, the function of peak reduction/displacement (peak cut/shift).Because above-mentioned is excellent It is adapted to fixed pattern battery from way to be particularly suitable for not turn-overing and wishing in stable state (for example it is possible to say Vibrate less state) under the nickel-zinc cell that processed.As the form of the nickel-zinc cell for these purposes, can enumerate Nickel-zinc cell (such as capacity is the battery of 40～200Wh), nickel-zinc cell module (for example more than 6 batteries), nickel-zinc cell system System (for example more than 6 nickel-zinc cell modules) etc., as long as adopt optimal form according to purposes.The nickel-zinc cell of the present invention It is not only nickel-zinc cell monomer, is configured to combine the battery system of solar electrical energy generation, msy be also constructed to and fuel electricity Pond (such as solid electrolyte fuel cell (SOFC), high molecular fuel battery (PEFC)) simultaneously sets use.

It is accompanied with the LDH dividing plate of porous substrate

As described above, the inorganic solid electrolyte body constituting dividing plate in the present invention can be membranaceous or stratiform form.This In the case of kind, be preferably made membranaceous or stratiform inorganic solid electrolyte body formed on porous substrate or therein, be accompanied with The dividing plate of porous substrate.The particularly preferred dividing plate being accompanied with porous substrate possesses porous substrate and is formed on this porous substrate And/or the carrier ring in porous substrate, carrier ring comprises aforesaid layered double-hydroxide (LDH).Carrier ring does not have permeable Property.That is, porous material can have water penetration because of the presence in hole, but carrier ring is by LDH, and densification is permeable to not having The degree of property.Carrier ring is preferably formed as on porous substrate.For example shown in Fig. 4, preferably with LDH dense film on porous substrate 28 Form formed carrier ring 20.In this case, naturally it is also possible to as shown in figure 4, many from the point of view of the property of porous substrate 28 The surface of hole base material 28 and its neighbouring in the hole also form LDH.Or it is also possible to as shown in Figure 5, in porous substrate 28 In (the such as surface of porous substrate 28 and its neighbouring in the hole) densely be formed LDH, thus make at least the one of porous substrate 28 Part constitutes carrier ring 20 '.For this point, the embodiment shown in Fig. 5 is the carrier ring eliminating Fig. 4 illustrated embodiment Be equivalent in 20 and constitute obtained by the part of film, but be not limited to this, as long as carrier ring is parallel with the surface of porous substrate 28 Exist.In a word, because carrier ring by LDH densification to the degree not having water penetration, it is possible to obtain there is hydroxide Thing ionic conductivity but there is no the peculiar function of water penetration.

Porous substrate is preferably able to form the base material of the carrier ring containing LDH thereon and/or wherein, to its material, porous Structure is not particularly limited.The carrier ring being formed on porous substrate and/or in porous substrate containing LDH is typical scenario, but Carrier ring containing LDH can be formed on nonporous substrate, then by various known methods by nonporous substrate porous.In a word, Porous substrate possesses the loose structure with water penetration, and can constitute electrolyte when being installed in battery as battery separator can Reach the structure of carrier ring, from this viewpoint, be preferred.

Porous substrate is preferably made up of at least one in ceramic material, metal material and macromolecular material.Porous base Material is more preferably made up of ceramic material.In this case, as the preference of ceramic material, can enumerate aluminium oxide, zirconium oxide, Titanium dioxide, magnesium oxide, spinelle, calcium oxide, cordierite, zeolite, mullite, ferrite, zinc oxide, carborundum, nitrogen Change aluminum, silicon nitride and their combination in any, more preferably aluminium oxide, zirconium oxide, titanium dioxide and their combination in any, spy You Xuanwei not aluminium oxide and zirconium oxide, most preferably aluminium oxide.During using these porous ceramicss, easily form compactness excellent Carrier ring containing LDH.As the preference of metal material, aluminum and zinc can be enumerated.As the preference of macromolecular material, permissible Enumerate polystyrene, polyether sulfone, polypropylene, epoxy resin, polyphenylene sulfide and their combination in any.More preferably from above-mentioned various Suitably it is selected as toleration, the i.e. excellent material of alkali resistance of the electrolyte to battery in preferred material.

The average air aperture of porous substrate is preferably 0.001～1.5 μm, more preferably 0.001～1.25 μm, excellent further Elect 0.001～1.0 μm as, particularly preferably 0.001～0.75 μm, most preferably 0.001～0.5 μm.By for such model Enclose it can be ensured that porous substrate has desired water penetration and forms densification to the degree without water penetration containing LDH Carrier ring.In the present invention, can be by, based on ultramicroscope (SEM) image on the surface of porous substrate, measuring gas The longest distance in hole is carrying out the mensure in average air aperture.Used in this mensure, the multiplying power of ultramicroscope (SEM) image is 20000 times, the whole pore footpaths obtaining are arranged by size order, below above 15 numerical value peace average of averaging 15 numerical value, add up to each visual field to take 30 numerical value, calculate the meansigma methodss in 2 visuals field, can obtain average air aperture.Survey length When, it is possible to use the long function of survey of the software of SEM, image analysis software (such as Photoshop, Adobe company system) etc..

The surface of porous substrate preferably has 10～60% porosity, and more preferably 15～55%, more preferably 20～50%.By for such scope it can be ensured that porous substrate have desired water penetration and formed fine and close to not There is the carrier ring containing LDH of the degree of water penetration.Herein, it is because easily using using the porosity on the surface of porous substrate Following image procossing carry out porosity mensure, and it may be said that the porosity on the surface of porous substrate substantially represent porous base The porosity within material.If i.e., it is possible to say that the surface of porous substrate is fine and close, the inside of porous substrate is similarly to cause Close.In the present invention, the porosity on the surface of porous substrate can measure as described below by using the method for image procossing. That is, 1) ultramicroscope (SEM) image (more than 10000 times of multiplying power) on acquirement porous substrate surface, 2) use Photoshop Image analysis softwares such as (Adobe company systems), the SEM image of reading tonal gradation, 3) press [image] → [tonal correction] → [two Value] sequentially built black and white bianry image, 4) with the pixel count shared by black portions divided by image whole pixel count institutes The value obtaining is the porosity (%).Should illustrate, carry out the mensure preferred pair porous substrate surface of the porosity by this image procossing The region of 6 μm of 6 μ m carry out, in order to be more objective index, more preferably obtain using to region at optional 3 The porosity meansigma methodss.

Carrier ring is formed on porous substrate and/or in porous substrate, is preferably formed as on porous substrate.Such as Fig. 4 institute Show, in the case that carrier ring 20 is formed on porous substrate 28, carrier ring 20 is the form of LDH dense film, this LDH dense film Typical case be to be formed by LDH.In addition, as shown in figure 5, in the case that carrier ring 20 ' is formed in porous substrate 28, many In hole base material 28 (typically the surface of porous substrate 28 and its near in the hole) densely be formed LDH, so carrier ring 20 ' are typically formed by least a portion in porous substrate 28 and LDH.Carrier ring 20 ' shown in Fig. 5 can by grind, The known methods such as cutting remove the part being equivalent to film in the carrier ring 20 shown in Fig. 4 and obtain.

Carrier ring does not have water penetration.Even if such as carrier ring one side in 25 DEG C contact with water one week also waterproof.That is, every Flaggy is by LDH densification to the degree without water penetration.But, in functional membrane local and/or contingently exist have It is also possible to be repaired by filling this defect with suitable healant (such as epoxy resin etc.) in the case of the defect of aqueouss To guarantee impermeability, such healant is not necessarily to hydroxide ion conductivity.In a word, carrier ring (typical case Be LDH dense film) surface preferably have less than 20% the porosity, more preferably less than 15%, more preferably Less than 10%, particularly preferably less than 7%.The porosity on the surface of carrier ring lower it is meant that carrier ring (typically LDH Dense film) compactness higher, be preferred.Herein, it is because easily using following using the porosity on the surface of carrier ring Image procossing carries out porosity mensure, and the porosity on the surface of carrier ring is it may be said that substantially represent the pore within carrier ring Rate.If i.e., it is possible to say that the surface of carrier ring is fine and close, the inside of carrier ring is similarly fine and close.In the present invention, every The porosity on the surface of flaggy can measure as described below by using the method for image procossing.That is, 1) obtain dividing plate layer surface Ultramicroscope (SEM) image (more than 10000 times of multiplying power), 2) using the image analysis such as Photoshop (Adobe company system) Software, read tonal gradation SEM image, 3) by [image] → [tonal correction] → [binaryzation] sequentially built black and white two Value image, 4) pixel count shared by with black portions divided by the value of whole pixel count gained of image as the porosity (%).Should Illustrate, the region being carried out 6 μm of 6 μ m of the mensure preferred pair dividing plate layer surface of the porosity by this image procossing is carried out, in order to It is more objective index, more preferably using the meansigma methodss to the porosity that region at optional 3 obtains.

Layered double-hydroxide is preferably made up of the aggregation of multiple platy particles (i.e. LDH platy particles), the plurality of plate Shape particle is to their the plate face direction orientation intersecting or obliquely intersect substantially vertical with the surface (substrate surface) of porous substrate. For embodiments thereof, as shown in figure 4, in the case of forming carrier ring 20 in the form of the LDH dense film on porous substrate 28, This embodiment is particularly preferred and attainable, but as shown in figure 5, (typically in porous substrate in porous substrate 28 28 surface and its neighbouring in the hole) densely be formed LDH, so that at least a portion of porous substrate 28 constitutes carrier ring In the case of 20 ', also can be achieved on.

I.e. it is known that LDH crystallization has：There is the form of the platy particles of the layer structure shown in Fig. 6, above-mentioned substantially vertical Or the orientation tilting is extremely advantageous characteristic for the carrier ring (such as LDH dense film) containing LDH.This is because after orientation Carrier ring containing LDH (being for example orientated LDH dense film) there is conductivity anisotropy, i.e. the side that LDH platy particles are orientated It is significantly higher than the conductivity in perpendicular direction to the hydroxide ion conductivity in (i.e. the direction parallel with LDH layer).Actual On, the present inventor etc. finds in the orientation block of LDH, and the conductivity (S/cm) of differently- oriented directivity is than the side vertical with differently- oriented directivity To high 1 digit of conductivity (S/cm).That is, the orientation of the above-mentioned substantially vertical or inclination in the carrier ring containing LDH of the present invention The conductivity anisotropy that LDH orientation body has (is hung down with the surface of carrier ring or porous substrate in thickness direction Straight direction) bring into play to greatest extent or intentionally as a result, the biography in thickness direction can be improved to greatest extent or intentionally Conductance.And, because the carrier ring containing LDH has a layer form, compared with the LDH of block form, it is capable of low resistance.Tool The carrier ring containing LDH having such orientation easily makes hydroxide ion conduct in thickness direction.And, because fine and close Change, so being extremely suitable for the dividing plate requiring high conductance and compactness are had on thickness direction.

Particularly preferably contain LDH platy particles in the carrier ring (typically LDH dense film) of LDH high in generally vertical direction Degree orientation.This is height-oriented can to confirm in the following way：Using X-ray diffraction method, the surface of carrier ring is being measured In the case of, essentially without the peak (003) crystal face is detected, or peak ratio (012) crystal face of (003) crystal face detecting Peak weak (but, using with result from (012) crystal face peak same position at observe diffraction maximum porous substrate situation Under because cannot determine result from LDH platy particles (012) crystal face peak, be not limited thereto).This feature peak is special Property represent the LDH platy particles constituting carrier ring with respect to carrier ring generally perpendicular direction (i.e. vertical direction or be similar to Vertical incline direction, preferred vertical) orientation.I.e. although the peak of known (003) crystal face is the LDH powder to No yield point Carry out observed highest peak in the case of X-ray diffraction, but in the case of the carrier ring containing orientation LDH, by making LDH Platy particles, with respect to carrier ring generally perpendicular direction orientation, essentially without the peak (003) crystal face is detected, or are examined The peak of peak ratio (012) crystal face of (003) crystal face measuring is weak.This is because c-axis direction (00l) crystal face belonging to (003) crystal face (l is 3 and 6) is the face parallel with the layer structure of LDH platy particles, so, if this LDH platy particles is with respect to dividing plate Layer generally perpendicular direction orientation, then, also towards generally perpendicular direction, result is by X-ray diffraction method for LDH layer structure In the case of measuring dividing plate layer surface, the peak of (00l) crystal face (l be 3 and 6) occurs without or is difficult to occur.Particularly (003) is brilliant There is following tendency at the peak in face, i.e. in the case of there is the peak of (003) crystal face, will than the peak intensity of (006) crystal face it is possible to Say compared with the peak of (006) crystal face, easily evaluate whether there is orientation in generally perpendicular direction.Therefore, the dividing plate containing orientation LDH Essentially without the peak (003) crystal face is detected or the peak of peak ratio (012) crystal face of (003) crystal face that detects is weak and dark for layer Show in the height-oriented of vertical direction it is possible to say that this is preferred.

The thickness of carrier ring is preferably less than 100 μm, more preferably less than 75 μm, more preferably less than 50 μm, special Not You Xuanwei less than 25 μm, most preferably less than 5 μm.By making it so thin, it is capable of the low resistance of dividing plate.Carrier ring Preferably it is formed as LDH dense film on porous substrate, in this case, the thickness of carrier ring is equivalent to LDH dense film Thickness.In addition, in the case that carrier ring is formed in porous substrate, the thickness of carrier ring is equivalent to by porous substrate at least A part and LDH formed composite bed thickness, carrier ring formed on porous substrate with therein in the case of, be equivalent to LDH Dense film and the gross thickness of above-mentioned composite bed.In a word, if such thickness, then it is capable of being suitable for battery use etc. Desired low resistance.Because the lower limit of the thickness of LDH alignment films is different according to purposes, it is not particularly limited, But in order to ensure as the compactedness to a certain degree required by the functional membranes such as dividing plate, preferred thickness is more than 1 μm, more preferably More than 2 μm.

The above-mentioned LDH dividing plate being accompanied with porous substrate can manufacture as follows：(1) prepare porous substrate, porous substrate is soaked by (2) , in aqueous solution of raw material, described aqueous solution of raw material is with the total concentration of 0.20～0.40mol/L (Mg containing magnesium ion for stain²⁺) and aluminium ion (Al³⁺), and comprise carbamide, (3) carry out hydrothermal treatment consists to porous substrate in aqueous solution of raw material, make to comprise the double hydroxide of stratiform The carrier ring of thing is formed on porous substrate and/or in porous substrate.

(1) preparation of porous substrate

As described above, porous substrate is preferably by least one structure in ceramic material, metal material and macromolecular material Become.Porous substrate is more preferably made up of ceramic material.In this case, as the preference of ceramic material, oxidation can be enumerated Aluminum, zirconium oxide, titanium dioxide, magnesium oxide, spinelle, calcium oxide, cordierite, zeolite, mullite, ferrite, zinc oxide, Carborundum, aluminium nitride, silicon nitride and their combination in any, more preferably aluminium oxide, zirconium oxide, titanium dioxide and they appoint Meaning combination, particularly preferably aluminium oxide and zirconium oxide, most preferably aluminium oxide.During using these porous ceramicss, exist and easily carry The tendency of the high compactness of carrier ring containing LDH.In the case of the porous substrate using ceramic material, preferred pair porous base Material is implemented ultrasound wave cleaning, is cleaned with ion exchange water.

On the other hand, in the case of using macromolecular material, preferably prepare surface by the polymer base material of anionic.Logical Cross surface anionic, make the group from anion generate the core of LDH in subsequent handling, LDH tabular grain can be promoted Son grows and to generally vertical direction orientation.As long as known method is passed through to can be cloudy by the polymer base material of anionic in surface The polymer base material of ionizing carries out anionic process and is prepared.Preferably by the surface tax to polymer base material Giving can be as the anion acquirement of LDH from SO₃ ^-(sulfonation), OH^-(hydroxylating) and CO₂ ^-At least one selecting in (carboxylated) Plant and carry out anionic process, more preferably sulfonation.The polymer base material being capable of anionic is preferably as the electricity to battery Solve the toleration of liquid and there is alkali resistance.The polymer base material being capable of anionic preferably comprises from polystyrene, polyether sulfone, gathers At least one selecting in propylene, epoxy resin, polyphenylene sulfide, these polymer base materials are particularly suitable for sulfonation.Particularly fragrance Family polymer base material is preferred because of easy anionic (particularly sulfonation), and such fragrant family polymer base material for example wraps Containing at least one selecting from polystyrene, polyether sulfone, epoxy resin, polyphenylene sulfide, most preferably comprise polystyrene.Carry out In the case that sulfonation is processed, as long as the polymer base material being possible to sulfonation is immersed in sulphuric acid (such as concentrated sulphuric acid), oleum, chlorine Sulfonic acid, sulfuric anhydride etc. are capable of in the acid of sulfonation can be it is also possible to utilize other sulfonation technologies.Dipping in the acid being capable of sulfonation As long as carrying out under room temperature or high temperature (such as 50～150 DEG C).In the case of fragrant family polymer base material, by sulphur The fragrant family polymer base material changed comes in the total reflection algoscopy (ATR) by Fourier transformation type infrared spectroscopy (FT-IR) In the case of measuring its surface, come from the 1601cm of phenyl CC stretching vibration in transmitted spectrum^-1Transmittance values T at place₁₆₀₁Divided by Come from sulfonic 1127cm^-1Transmittance values T at place₁₁₂₇Obtained from value T₁₆₀₁/T₁₁₂₇It is preferably more than 0.920, more preferably More than 0.930, more preferably more than 0.940.In transmitted spectrum, in 1601cm^-1The absorbance at the extinction peak that place observes Value T₁₆₀₁Because being derived from phenyl CC stretching vibration, regardless of whether there being sulfonic group, all for identical value, and in 1127cm^-1 Transmittance values T at the extinction peak that place observes₁₁₂₇Because being derived from sulfonic group, the density of sulfonic acid is higher, and value is lower.Cause This, T₁₆₀₁/T₁₁₂₇Value bigger, more densely there are multiple sulfonic groups on the surface of polymer base material, can give birth to high-density Become：Introduce sulfonic group as the core of the LDH of intermediate layer anion, contribute to the densification of the carrier ring containing LDH.Therefore, exist By during polymer base material sulfonation, by the time of suitable adjustment dipping in the acid being capable of sulfonation, above-mentioned T can be made₁₆₀₁/T₁₁₂₇ Value within the above range.For example in the case of carrying out sulfonation process using concentrated sulphuric acid, preferably dip time is more than 6 days, more It is preferably more than 12 days.The polymer base material implementing anionic like this is preferably cleaned with ion exchange water, then in room It is dried under temperature or high temperature (such as 30～50 DEG C).

(2) dipping in aqueous solution of raw material

Next, porous substrate is immersed in aqueous solution of raw material towards (for example horizontally or vertically) with desired.Will In the case that porous substrate level keeps, only need to configure porous substrate in the way of suspention, suspension are contacted with container bottom is Can, for example porous substrate can be fixed with the state being suspended in aqueous solution of raw material from container bottom.By porous substrate In the case of vertical holding, as long as can be by vertically disposed for porous substrate fixture in container bottom setting.In a word, preferably Make LDH on porous substrate with generally vertical direction or (i.e. LDH platy particles are towards their plate face close to vertical direction The substantially vertical direction intersecting or obliquely intersecting in surface (substrate surface) with porous substrate) composition that grows or configuration.Raw material Aqueous solution includes magnesium ion (Mg with the total concentration specifying²⁺) and aluminium ion (Al³⁺), and comprise carbamide.Urinated by existing Element, can generate ammonia in the solution using hydrolysis of urea, thus improve pH value, make the metal ion coexisting form hydroxide Thing is such that it is able to obtain LDH.In addition, because with hydrolysis produce carbon dioxide, it is possible to obtain anion be carbonate from The LDH of subtype.Magnesium ion and aluminum ions total concentration (Mg that aqueous solution of raw material is comprised²⁺+Al³⁺) preferably 0.20～ 0.40mol/L, more preferably 0.22～0.38mol/L, more preferably 0.24～0.36mol/L, particularly preferably 0.26 ～0.34mol/L.If the concentration in such scope, then can balance and carry out karyogenesis and crystalline growth, energy well Access that not only orientation is excellent but also the carrier ring containing LDH that compactness is also excellent.If i.e. it is believed that magnesium ion and aluminium ion Total concentration low, then compared with karyogenesis, crystalline growth is top dog, population reduce, particle size increase, and if This total concentration is high, then, compared with crystalline growth, karyogenesis are top dog, and population increases, and particle size reduces.

Preferably magnesium nitrate and aluminum nitrate are dissolved in aqueous solution of raw material so that aqueous solution of raw material except magnesium ion and Aluminium ion, also comprises nitrate ion.In the case of being somebody's turn to do, in aqueous solution of raw material, carbamide is with respect to nitrate ion (NO₃ ^-) rub You are than (carbamide/NO₃ ^-) it is preferably 2～6, more preferably 4～5.

(3) form the carrier ring containing LDH by hydrothermal treatment consists

In aqueous solution of raw material, hydrothermal treatment consists are carried out to porous substrate, formed on porous substrate and/or in porous substrate Carrier ring containing LDH.This hydrothermal treatment consists is carried out preferably in hermetic container and at 60～150 DEG C, and more preferably 65～120 DEG C, more preferably 65～100 DEG C, particularly preferably 70～90 DEG C.As long as the ceiling temperature of hydrothermal treatment consists selects porous base Material (such as polymer base material) is notheated the temperature of the degree of deformation.Programming rate during hydrothermal treatment consists does not especially limit Fixed, can be for example 10～200 DEG C/h, preferably 100～200 DEG C/h, more preferably 100～150 DEG C/h.Hydrothermal treatment consists when As long as between suitably determined according to the target density of the carrier ring containing LDH and target thickness.

Preferably after hydrothermal treatment consists, take out porous substrate from hermetic container, be carried out with ion exchange water.

The LDH platy particles high compaction of the carrier ring containing LDH in the composite containing LDH manufacturing as described above Change, and to the generally vertical direction orientation favourable to conduction.Therefore, it can be said that be extremely applicable to zinc dendrite develops into reality With changing the nickel-zinc cell of maximum barrier.

But, the two sides of porous substrate can be formed at by the carrier ring containing LDH that above-mentioned manufacture method obtains.Cause This, in order to the composite containing LDH is made to be suitable as the form of dividing plate, preferably after film forming to porous substrate one The carrier ring containing LDH in face carries out mechanical grinding, or takes and can not form arranging of carrier ring containing LDH during film forming in one side Apply.

The manufacture method of LDH dense plates

As the preferred configuration of the inorganic solid electrolyte of tabular, layered double-hydroxide (LDH) DB can be enumerated. LDH DB can be made by all of method, below an embodiment of preferable production process is illustrated.This system The method of making is carried out as follows：By the material powder molding of the LDH with brucite as representative and burn till and make oxide sintered body, will After it is regenerated as layered double-hydroxide, remove unnecessary moisture.According to the method, can easy and stably provide and manufacture Relative density is more than 88% high-grade layered double-hydroxide DB.

(1) preparation of material powder

Prepare formula：M²⁺ _1-xM³⁺ _x(OH)₂A^n- _x/n·mH₂O (in formula, M²⁺For the cation of divalent, M³⁺For trivalent sun from Son, A^n-For the anion of n valency, n is more than 1 integer, and x is 0.1～0.4, m is arbitrary real number) shown in the double hydrogen-oxygen of stratiform The powder of compound is as material powder.In above-mentioned formula, M²⁺Can be arbitrary divalent cation, as preference, can enumerate Mg²⁺、Ca²⁺And Zn²⁺, more preferably Mg²⁺.M³⁺Can be arbitrary trivalent cation, as preference, Al can be enumerated³⁺Or Cr³⁺, more preferably Al³⁺.A^n-Can be arbitrary anion, as preference, OH can be enumerated^-And CO₃ ^2-.Therefore, above-mentioned Formula preferably at least M²⁺Comprise Mg²⁺、M³⁺Comprise Al³⁺、A^n-Comprise OH^-And/or CO₃ ^2-.N is more than 1 integer, preferably 1 or 2.X is 0.1～0.4, preferably 0.2～0.35.Such material powder can be commercially available layered double-hydroxide product, It can be the raw material making by using the known method such as nitrate or muriatic liquid phase synthesizing method.The particle diameter of material powder As long as can get desired layered double-hydroxide DB just not limit, volume reference D50 mean diameter is preferably 0.1 ～1.0 μm, more preferably 0.3～0.8 μm.This is because when the particle diameter of material powder is meticulous, powder easily condenses, residual during molding Stay the probability of pore high；When excessive, mouldability is deteriorated.

Material powder pre-burning can be made oxide powder as needed.Calcined temperature now is according to the M constituting²⁺ And M³⁺And have differences, preferably less than 500 DEG C, more preferably 380～460 DEG C, enter in the region of the little amplitude variation of raw material particle size OK.

(2) making of molded body

Material powder molding is obtained molded body.This molding is preferably by the molded body after molding and before burning till (hereinafter referred to as For molded body) relative density be 43～65%, more preferably 45～60%, more preferably 47%～58%, using example Carry out as extrusion forming.The relative density of molded body is to calculate density by the size of molded body and weight, divided by solid density And obtain, but the weight of molded body is because affected by adsorption moisture, and in order to obtain unique value, preferred pair uses The relative density of the molded body that the material powder of more than 24 hours is made is deposited in room temperature, exsiccator below 20% for the relative humidity After being measured or molded body being deposited under these conditions, relative density is measured.But, by material powder pre-burning And in the case of making oxide powder, the relative density of molded body is preferably 26～40%, more preferably 29～36%.Should Illustrate, tried to achieve as follows using relative density during oxide powder：Assume to constitute each metal unit of layered double-hydroxide Procatarxis pre-burning and be changed into oxide respectively, obtain reduction density as each hopcalite, with this reduction density as denominator And obtain.The extrusion forming enumerated as one can be carried out it is also possible to utilize cold isostatic pressing using the compacting of mould single shaft (CIP) carry out.In the case of cold isostatic pressing (CIP), preferably material powder is put into and in rubber container, carry out vacuum Seal or use preform.Furthermore, it is possible to carry out molding with the known method such as injection forming, extrusion molding, with regard to becoming Type method is not particularly limited.But, in the case that oxide powder is made in material powder pre-burning, it is defined in dry formed Method.The relative density of these molded bodys not only has an impact to the intensity of the DB obtaining, and to generally having plate-like shape The degree of orientation of layered double-hydroxide also have an impact, it is therefore preferable that considering its purposes etc. and suitably setting within the above range Relative density during molding.

(3) firing process

The molded body obtaining in above-mentioned operation is burnt till and is obtained oxide sintered body.This burns till preferably by oxide The weight of sintered body is the 57～65% of the weight of molded body and/or volume is carried out for the 70～76% of the volume of molded body. If more than the 57% of the weight of molded body, then subsequent handling is regenerated as during layered double-hydroxide being difficult generation regenerating Out-phase；If less than 65%, then fully burnt till and in subsequent handling fully densification.In addition, if being molding More than the 70% of the volume of body, then subsequent handling be regenerated as during layered double-hydroxide being difficult generating out-phase, and be not easy to produce Raw crackle；If less than 76%, then fully burnt till and in subsequent handling fully densification.By material powder pre-burning In the case of making oxide powder, preferably obtain the weight of molded body the volume of 85～95% and/or molded body 90% Above oxide sintered body.No matter whether material powder is changed by oxide for oxide sintered body it is preferably to burn till by pre-burning The relative density calculated is 20～40%, more preferably 20～35%, more preferably 20～30%.Herein, change by oxide The relative density calculated is tried to achieve as follows：Assume that each metallic element constituting layered double-hydroxide is changed into oxygen respectively because burning till Compound, obtains reduction density as each hopcalite, obtains relative density with this reduction density as denominator.For Preferred firing temperature to oxide sintered body is 400～850 DEG C, more preferably 700～800 DEG C.Preferably within the range Keep more than 1 hour under firing temperature, the preferred retention time is 3～10 hours.In addition, in order to prevent because of intensification drastically Release moisture, carbon dioxide and make molded body ftracture, for making it reach the intensification of above-mentioned firing temperature preferably with 100 DEG C/h Speed below is carried out, more preferably 5～75 DEG C/h, more preferably 10～50 DEG C/h.Therefore, from being warming up to cooling (100 Below DEG C) total firing time preferably ensure that more than 20 hours, more preferably 30～70 hours, more preferably 35～65 Hour.

(4) it is regenerated as the operation of layered double-hydroxide

The oxide obtaining in above-mentioned operation sintered body is maintained at the above-mentioned anion (A comprising n valency^n-) aqueous solution in Or directly over aqueous solution, it is regenerated as layered double-hydroxide, thus obtain the layered double-hydroxide firming body rich in moisture. That is, necessarily comprise unnecessary moisture using the layered double-hydroxide firming body that this preparation method obtains.Should illustrate, wrap in aqueous solution The anion containing can be the anion of the same race with the anion that comprises in material powder or different types of cloudy from Son.Holding in aqueous or directly over aqueous solution for the oxide sintered body preferably utilizes hydrothermal synthesis method in hermetic container Carry out, as the example of such hermetic container, the hermetic container that Teflon (registered trade mark) is made can be enumerated, be more preferably it Outside possesses the hermetic container of the sleeve pipes such as stainless steel.Layered double-hydroxide is preferably as follows and carries out：By oxide sintered body At 20 DEG C less than at 200 DEG C, kept with the state that at least one side of oxide sintered body is contacted with aqueous solution, more Preferably temperature is 50～180 DEG C, and further preferred temperature is 100～150 DEG C.Preferably in such layered double-hydroxide Oxidate sintered body is kept more than 1 hour at a temperature of change, more preferably 2～50 hours, more preferably 5～20 hours.As Fruit is such retention time, then it can be made fully to be regenerated as layered double-hydroxide and avoid or reduce out-phase residual.Should Give explanation, though this retention time long also have no problem, as long as pay attention to efficiency set in good time.

As the anion species of the aqueous solution being regenerated as the anion comprising n valency that layered double-hydroxide uses, false Surely be in the air carbon dioxide (carbanion) in the case of, ion exchange water can be used.Should illustrate, in hermetic container During interior hydrothermal treatment consists, oxide sintered body can be made to submerge in aqueous solution, it is possible to use fixture with least one side with water-soluble The state of liquid contact is processed.In the case of the state processing being contacted with aqueous solution with least one side, because not having with complete water Compare unnecessary water quantities less, so subsequent handling completes sometimes at short notice.But, because easy when aqueous solution is very few Crack, it is advantageous to using the moisture above on an equal basis with burning till body weight.

(5) dehydration procedure

Unnecessary moisture is removed in the layered double-hydroxide firming body rich in moisture obtaining from above-mentioned operation.So Can get the layered double-hydroxide DB of the present invention.The operation of the unnecessary moisture of this removing is preferably below 300 DEG C, removing Carry out under the environment of presumption relative humidity more than 25% under the maximum temperature of operation.In order to prevent moisture from the double hydroxide of stratiform Sharp evaporate in thing firming body, in the case of being dehydrated at temperatures greater than room temperature, preferably enclose again and be regenerated as stratiform pair Carry out in hermetic container used in the step for regeneration of hydroxide.Preferable temperature now is 50～250 DEG C, further preferably For 100～200 DEG C.In addition, preferred relative humidity during dehydration is 25～70%, more preferably 40～60%.Can To be dehydrated at room temperature, as long as relative humidity now does not just have in the range of 40～70% in common indoor environment Problematic.

Embodiment

The present invention is specifically described further by following example.

Example 1：It is accompanied with the making of LDH dividing plate and the evaluation of porous substrate

(1) making of porous substrate

Boehmite (Sasol company system, DISPAL 18N4-80), methylcellulose and ion exchange water are pressed (Bo Mu Stone)：(methylcellulose)：The mass ratio of (ion exchange water) is 10：1：5 are weighed, and are then kneaded.Pressed using manual Power machine carries out extrusion molding to the mixing thing obtaining, and is shaped to size well beyond 5cm × 8cm and thickness is the tabular of 0.5cm. By the molded body obtaining after 80 DEG C of dryings 12 hours, burn till 3 hours at 1150 DEG C, obtain aoxidizing aluminum porous substrate.By this The porous substrate cutting off processing that sample obtains becomes the size of 5cm × 8cm.

For the porous substrate obtaining, by using the method for image procossing, measure the porosity on porous substrate surface, knot Fruit is 24.6%.Being determined as follows of this porosity is carried out：1) scanning electron microscope (SEM, JSM-6610LV, JEOL are used Company system), surface micro-structure is observed with the accelerating potential of 10～20kV, obtains the ultramicroscope (SEM) on porous substrate surface Image (more than 10000 times of multiplying power), 2) using image analysis softwares such as Photoshop (Adobe company system), read tonal gradation SEM image, 3) by [image] → [tonal correction] → [binaryzation] sequentially built black and white bianry image, 4) by black part Divide shared pixel count divided by the value of the total pixel number gained of image as the porosity (%).6 μ m 6 to porous substrate surface μm region implement the mensure of this porosity.Should illustrate, the SEM image on porous substrate surface is shown in Fig. 7.

In addition, measuring the average air aperture of porous substrate, result is about 0.1 μm.In the present invention, by with porous substrate Based on ultramicroscope (SEM) image on surface, measure the mensure to carry out average air aperture for the longest distance of pore.This survey Used in fixed, the multiplying power of ultramicroscope (SEM) image is 20000 times, and the whole pore footpaths obtaining are arranged by size order Row, 15 numerical value below above 15 numerical value peace average of averaging, add up to each visual field to take 30 numerical value, calculate 2 The meansigma methodss in the individual visual field, obtain average air aperture.Survey in length, using the long function of the survey of the software of SEM.

(2) cleaning of porous substrate

By the porous substrate obtaining, ultrasound wave cleans 5 minutes in acetone, ultrasound wave cleaning 2 minutes in ethanol, then, In ion exchange water, ultrasound wave cleans 1 minute.

(3) making of aqueous solution of raw material

As raw material, prepare magnesium nitrate hexahydrate (Mg (NO₃)₂·6H₂O, Kanto Kagaku K. K.'s system), nitric acid Aluminum nonahydrate (Al (NO₃)₃·9H₂O, Kanto Kagaku K. K.'s system) and carbamide ((NH₂)₂CO, Sigma-Aldrich system). By cation ratio (Mg²⁺/Al³⁺) it is 2 and total metal ion molar concentration (Mg²⁺+Al³⁺) it is 0.320mol/L, weigh magnesium nitrate six Hydrate and aluminum nitrate nonahydrate, and put into beaker, add ion exchange water wherein, make total amount be 75ml.Stirring obtains Solution after, will be by carbamide/NO₃ ^-The carbamide that=4 ratio weighs is added in solution, stirs further, obtains raw material water-soluble Liquid.

(4) pass through hydrothermal treatment consists film forming

The porous substrate cleaning in the aqueous solution of raw material making in above-mentioned (3) and above-mentioned (2) is together enclosed Teflon In (registered trade mark) hermetic container processed (internal volume 100ml, outside are stainless steel sleeve pipe).Now, make base material from Teflon (note Volume trade mark) bottom of hermetic container processed floated and fixes, be horizontally disposed with the way of solution contacted substrate two sides.Then, pass through Implement 168 hours (7 days) hydrothermal treatment consists at 70 DEG C of hydrothermal temperature, form layered double-hydroxide alignment films in substrate surface (carrier ring).After the stipulated time, base material is taken out from hermetic container, is cleaned with ion exchange water, in 70 DEG C of dryings 10 Hour, the dense film (hereinafter referred to as film sample) of layered double-hydroxide (hereinafter referred to as LDH) is obtained on base material.The film obtaining The thickness of sample is of about 1.5 μm.Thus obtain (the hereinafter referred to as composite wood of the composite sample containing layered double-hydroxide Material samples).Should illustrate, LDH film is formed at the two sides of porous substrate, but, in order that composite has as dividing plate Form, carries out mechanical grinding to the LDH film of the one side of porous substrate.

(5) various evaluations

(5a) identification of film sample

Using X-ray diffraction device (company system RINT TTR III of science), in voltage：50kV, current value：300mA, survey Determine scope：Under 10～70 ° of condition determination, the crystalline phase of film sample is measured, obtains the XRD spectrum shown in Fig. 8.For The XRD spectrum obtaining, using the layered double-hydroxide (hydrotalcite-based compound) described in JCPDS Card NO.35-0964 Diffraction maximum identified.Result is it is thus identified that film sample is layered double-hydroxide (LDH, hydrotalcite-based compound).Should say Bright, in the XRD spectrum shown in Fig. 8, also observe in the lump to come from and constitute the aluminium oxide of porous substrate being formed with film sample Peak (peak of in figure band zero labelling).

(5b) observation of micro structure

Using scanning electron microscope (SEM, JSM-6610LV, JEOL company system), with the accelerating potential of 10～20kV, The surface micro-structure of film sample is observed.The SEM image (secondary electron image) of the surface micro-structure of film sample obtaining shows In Fig. 9.

In addition, grind the section of grinding composite material sample by CP, formed and grind section, shown using scanning electron Micro mirror (SEM), observe the micro structure in this grinding section with the accelerating potential of 10～20kV.The composite sample so obtaining The SEM image grinding section micro structure is shown in Figure 10.

(5c) mensure of the porosity

For film sample, by using the method for image procossing, measure the porosity on film surface.The mensure of this porosity is such as Under carry out：1) use scanning electron microscope (SEM, JSM-6610LV, JEOL company system), with the accelerating potential of 10～20kV Observation surface micro-structure, ultramicroscope (SEM) image (more than 10000 times of multiplying power) on the surface of acquirement film, 2) use The image analysis softwares such as Photoshop (Adobe company system), the SEM image of reading tonal gradation, 3) press [image] → [tone Revise] the bianry image of → sequentially built black and white of [binaryzation], 4) will be total divided by image for the pixel count shared by black portions The value of pixel count gained is as the porosity (%).The mensure of this porosity is implemented to the region of 6 μm of 6 μ m of alignment layer surface. As a result, the porosity on the surface of film is 19.0%.In addition, using the porosity on this film surface, according to D=100%- (film surface The porosity) calculate density D (hereinafter referred to as surface film density) when film surface observation, result is 81.0%.

In addition, for film sample, also measuring the porosity grinding section.The mensure of the porosity in this grinding section, except Order as shown in above-mentioned (5b), obtains ultramicroscope (SEM) image (multiplying power of the section abradant surface of thickness direction in film More than 10000 times) outward, carry out in the same manner as the porosity on above-mentioned film surface.This pore is implemented to the film part in alignment films section Rate measures.Calculated by the section abradant surface of film sample like this porosity average out to 3.5% (3 section abradant surfaces average Value) although it is thus identified that being on porous substrate, defining the very high film of density.

(5d) fine and close sex determination test

Possess the compactness of water penetration degree in order to confirm film sample to have not, carried out fine and close sex determination as described below Test.First, as shown in Figure 11 A, the film of the composite sample 120 (being cut into 1cm × 1cm square) obtaining in above-mentioned (1) Sample side, is bonded in the silicone rubber 122 that there is the peristome 122a of 0.5cm × 0.5cm square in central authorities, the sandwich obtaining is used 2 Individual acrylic container 124,126 clamps and engages.The acrylic container 124 in silicone rubber 122 side for the configuration is bottomless, by this silicon Rubber 122 is engaged with acrylic container 124 with the open state of its peristome 122a.On the other hand, configuration is in composite The acrylic container 126 of the porous substrate side of sample 120 has bottom, injects ion exchange water 128 in this container 126.Now, Al and/or Mg can also be made to be dissolved in ion exchange water.That is, each component parts are configured to by running up and down after assembling Fall, make ion exchange water 128 contact the porous substrate side of composite sample 120.After these component parts etc. are assembled, measure Gross weight.Should illustrate, the passage (not illustrating) of closing is certainly formed with container 126, is unlocked after turning upside down. As shown in Figure 11 B, assembly is turned upside down and configured, after keeping 1 week in 25 DEG C, measure gross weight again.Now, in Asia In the case that the inner side surface of gram force container 124 has water droplet, wipe this water droplet.Then, calculate the gross weight before and after test Difference, thus judges consistency.As a result, even if after keeping 1 week at 25 DEG C, the weight that ion exchange water is also not observed becomes Change.Thereby confirm that film sample (i.e. functional membrane) has the high compactness of the degree not possessing water penetration.

Example 2：The making of nickel-zinc cell and evaluation

(1) it is accompanied with the preparation of the dividing plate of porous substrate

By the order same with example 1, as the dividing plate being accompanied with porous substrate, prepare hydrotalcite film on aluminum oxide base material (size：5cm×8cm).

(2) making of positive plate

Prepare to the addition of the nickel hydroxide particle of zinc and cobalt in the way of becoming solid solution.By this nickel hydroxide particle hydrogen Cobalt oxide is coated to and obtains positive active material.2% aqueous solution of the positive active material obtaining and carboxymethyl cellulose is mixed Close and prepare paste.It is 50% by the porosity rate of positive active material, formed in the metal porous substrate of nickel by porosity rate about 95% Collector on be equably coated with paste obtained above, be dried, obtain being coated with active substance in the region of 5cm × 5cm Partial positive plate.Now, adjust coating weight, make to comprise in active substance to be equivalent to the nickel hydroxide particle of 4Ah.

(3) making of negative plate

On the collector being formed by copper punch metal, coating comprises Zinc oxide powder 80 weight portion, zinc powder 20 weight Part and the mixture of polytetrafluoroethylparticle particle 3 weight portion, obtain being coated with about 50% porosity rate, in the region of 5cm × 5cm The negative plate of active substance part.Now, adjust coating weight, make the oxygen comprising in active substance to be equivalent to positive plate capacity 4Ah Change zinc powder.

(4) assembling of battery

Using positive plate obtained above, negative plate and the dividing plate being accompanied with porous substrate, by order dress shown below Nickel-zinc cell shown in figure 1.

First, prepare to pull down the ABS resin cuboid housing main body of outer casing upper cover.Near the central authorities of this housing main body Insertion is accompanied with the dividing plate (hydrotalcite film on aluminum oxide base material) of porous substrate, and its 3 side is fixed on using commercially available binding agent The inwall of housing main body.Positive plate and negative plate are inserted cathode chamber and anode chamber respectively.Now, with positive electrode collector and negative pole Collector configures positive plate and negative plate with the direction of housing main body contact internal walls.Fully flooded positive active material coating part The KOH aqueous solution of the 6mol/L of amount dividing is indoor as electrolyte injection positive pole.The liquid level of cathode chamber is away from outer casing bottom about 5.2cm.On the other hand, not only will fully flood negative electrode active material coated portion but also consider and estimate the minimizing when charging The 6mol/L of the excess quantity of water quantities KOH aqueous solution indoor as electrolyte injection negative pole.Liquid level in anode chamber Away from outer casing bottom about 6.5cm.The portion of terminal of positive electrode collector and negative electrode collector is connected with the outside terminal of shell upper respectively Connect.Outer casing upper cover is fixed on housing main body by heat bonding, by battery case container closure.Thus obtain nickel zinc electricity Pond.Should illustrate, because in this battery, the size of dividing plate is width 5cm × height 8cm, and, the work of positive plate and negative plate Property material coated portion size be width 5cm × height 5cm, so the top of cathode chamber and anode chamber is equivalent to the sky of 3cm Between be properly termed as side of the positive electrode remaining space and negative side remaining space.

(5) evaluate

To be equivalent to the electric current of the 0.4mA of the 0.1C of design capacitance 4Ah, made nickel-zinc cell is implemented with 10 hours perseverances Current charge.After charging, casing deformation is not observed, electrolyte spills.Observe the electrolyte content after charging, find cathode chamber , apart from outer casing bottom about 7.5cm, the liquid level of the electrolyte of anode chamber is apart from outer casing bottom about for the liquid level of electrolyte 5.2cm.By charging, cathode chamber electrolyte increases, and anode chamber electrolyte reduces, but has in negative electrode active material coated portion The positive active material of coating and negative electrode active material, by discharge and recharge, sufficient charge and discharge by enough electrolyte can occur The electrolyte of electricity reaction is maintained inside the shell.

Claims (16)

1. a kind of nickel-zinc cell, it comprises：

Positive pole, described positive pole contains nickel hydroxide and/or hydroxy nickel oxide,

Anode electrolyte, described anode electrolyte contains alkali metal hydroxide, impregnates described positive pole,

Negative pole, described negative pole contains zinc and/or zinc oxide,

Electrolyte liquid, described electrolyte liquid contains alkali metal hydroxide, impregnates described negative pole,

Hermetic container, described hermetic container accommodates described positive pole, described anode electrolyte, described negative pole and described electrolyte Liquid,

Dividing plate, described dividing plate has hydroxide ion conductivity but does not have water penetration, is arranged in described hermetic container The cathode chamber of described positive pole and described anode electrolyte and the anode chamber accommodating described negative pole and described electrolyte liquid will be accommodated Zoning is opened.

2. nickel-zinc cell according to claim 1, wherein, has side of the positive electrode remaining space, this is just in described cathode chamber The volume of pole side remaining space allows the water quantities increase and decrease producing with positive pole reaction during discharge and recharge, and, described negative There is in pole room negative side remaining space, the volume of this negative side remaining space allows with negative reaction during discharge and recharge to produce Raw water quantities subtracts increasing.

3. nickel-zinc cell according to claim 2, wherein, described side of the positive electrode remaining space has to exceed to be estimated with charging When positive pole reaction and increase water quantities volume, be not pre-charged with described anolyte in this side of the positive electrode remaining space Liquid, and, described negative side remaining space has to exceed and estimates the appearance of water quantities reducing with negative reaction when charging Long-pending, this negative side remaining space is pre-filled with the described electrolyte liquid of the amount estimating minimizing.

4. the nickel-zinc cell according to Claims 2 or 3, wherein, described side of the positive electrode remaining space have exceed estimate with The volume of the water quantities that positive pole during electric discharge reacts and reduces, is pre-filled with this side of the positive electrode remaining space and estimates minimizing Amount described anode electrolyte, and, described negative side remaining space have exceed estimate with electric discharge when negative reaction and The volume of increased water quantities, is not pre-charged with described electrolyte liquid in this negative side remaining space.

5. the nickel-zinc cell according to any one of claim 2～4, wherein, does not have in described side of the positive electrode remaining space There is the described positive pole of filling, and/or do not fill described negative pole in described negative side remaining space.

6. the nickel-zinc cell according to any one of claim 2～5, wherein, described dividing plate is longitudinally disposed, described just The top of pole room has described side of the positive electrode remaining space, and, it is remaining empty to have described negative side above described anode chamber Between.

7. the nickel-zinc cell according to any one of claim 1～6, wherein, described dividing plate is by inorganic solid electrolyte Body is formed.

8. nickel-zinc cell according to claim 7, wherein, the relative density of described inorganic solid electrolyte body be 90% with On.

9. the nickel-zinc cell according to claim 7 or 8, wherein, described inorganic solid electrolyte body comprises basic composition is Formula：M²⁺ _1-xM³⁺ _x(OH)₂A^n- _x/n·mH₂The layered double-hydroxide of O, in formula, M²⁺For the cation of divalent, M³⁺Sun for trivalent Ion, A^n-For the anion of n valency, n is more than 1 integer, and x is 0.1～0.4, m is arbitrary real number.

10. nickel-zinc cell according to claim 8, wherein, in described formula, M²⁺Comprise Mg²⁺, M³⁺Comprise Al³⁺, A^n- Comprise OH^-And/or CO₃ ^2-.

11. nickel-zinc cells according to any one of claim 7～10, wherein, described inorganic solid electrolyte body tool There is the form of tabular, membranaceous or stratiform.

12. nickel-zinc cells according to any one of claim 1～11, wherein, in the one or two sides of described dividing plate Also comprise porous substrate.

13. nickel-zinc cells according to claim 12, wherein, described inorganic solid electrolyte body is membranaceous or the shape of stratiform State, this membranaceous or stratiform inorganic solid electrolyte body is formed on described porous substrate or in described porous substrate.

14. nickel-zinc cells according to any one of claim 7～13, wherein, described inorganic solid electrolyte body leads to Cross hydrothermal treatment consists and be densified.

15. nickel-zinc cells according to any one of claim 1～14, wherein, described alkali metal hydroxide is hydrogen Potassium oxide.

16. nickel-zinc cells according to any one of claim 1～15, it also comprises：With the setting of described positive contact Positive electrode collector and with described cathode contact setting negative electrode collector.